Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/52—Two oxygen atoms
  • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals

Definitions

• the present invention relates to a process for preparing 1-alkyl-3-phenyluracils of the formula I
• R 1 is as defined above, and
• 1-Alkyl-3-phenyluracils of the general formula I are known in principle from WO 01/83459. They can be prepared as taught in WO 01/83459.
• N-alkylations at the free uracil nitrogen atom by reacting a uracil compound with an alkylating agent are described, for example, in U.S. Pat. No. 4,943,309.
• R 1 is as defined above and
• L 1 is a nucleophilically displaceable leaving group are reacted with one another
• the present invention relates to a process for preparing 1-alkyl-3-phenyluracils of the formula I which comprises the reaction of 3-phenyluracils of the formula II and alkylating agents of the formula III, wherein during the entire reaction the pH is kept in a range from 1 to 6 by adding base a little at a time.
• the process according to the invention affords 1-alkyl-3-phenyluracils of the formula I in high yields and high purities.
• the 1-alkyl-3-phenyluracils of the formula I may contain one or more centers of chirality, in which case they are present as enantiomers or diastereomer mixtures.
• the invention provides a process for preparing both the pure enantiomers or diastereomers and their mixtures.
• the 1-alkyl-3-phenyluracils of the formula I may also be present in the form of their agriculturally useful salts, the type of salt generally being immaterial. Suitable are, in general, the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the herbicidal action of the compounds I.
• Suitable cations are in particular ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium, where, if desired, one to four hydrogen atoms may be replaced by C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2-(2-hydroxyeth-1-oxy)eth-1-ylammonium, di(2-hydroxyeth-1-yl)ammonium, trimethylbenzylam
• Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, nitrate, hydrogencarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C 1 -C 4 -alkanoic acids, preferably formate, acetate, propionate and butyrate.
• organic moieties mentioned for the substituents R 1 -R 7 or as radicals on phenyl rings are collective terms for individual enumerations of the individual group members.
• All hydrocarbon chains, i.e. all alkyl, haloalkyl, alkoxy, alkenyl and alkynyl moieties, can be straight chain or branched.
• halogenated substituents preferably carry one to five identical or different halogen atoms. Halogen means in each case fluorine, chlorine, bromine or iodine.
• variables R 1 to R 6 have the following meanings, in each case on their own or in combination:
• R 1 is C 1 -C 4 -alkyl
• R 2 is hydrogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl
• R 3 is hydrogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl
• R 4 is hydrogen or halogen
• R 5 is halogen, cyano or C 1 -C 4 -haloalkyl
• R 6 is hydrogen or C 1 -C 4 -alkyl
• R 7 is hydrogen or C 1 -C 4 -alkyl
• R 2 has the following meanings:
• R 2 is hydrogen or C 1 -C 6 -haloalkyl
• R 2 has the following meanings:
• R 2 is C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl
• R 4 has the following meanings:
• R 4 is hydrogen or halogen
• 1-alkyl-3-phenyluracils of the formula I.a (corresponds to formula I where R 2 ⁇ CF 3 , R 3 ⁇ H and R 7 ⁇ CH 3 ), in particular the 1-alkyl-3-phenyluracils I.a.1 to I.a.24 of Table 1, are prepared, where the definitions of the variables R 1 , R 4 , R 5 and R 6 are of particular importance for the process according to the invention not only in combination with one another but in each case also on their own.
• the process according to the invention comprises the reaction of 3-phenyluracils of formula II and alkylating agents of the formula III wherein during the entire reaction the pH is kept in a range from 1 to 6 by adding base a little at a time:
• the group L 1 in the alkylating agent of the formula III is a nucleophilically displaceable leaving group
• 3-phenyluracils of the formula II are known from WO 01/83459 and WO 04/39768 and can be prepared in accordance with the literature cited.
• Preferred alkylating agents are C 1 -C 6 -alkyl halides, di-C 1 -C 6 -alkyl sulfates, di-C 1 -C 6 -alkyl carbonates, C 1 -C 6 -alkylsulfonic acids, C 1 -C 4 -alkyl C 1 -C 6 -alkyl sulfonates, C 1 -C 6 -haloalkylsulfonic acids, C 1 -C 4 -alkyl C 1 -C 6 -haloalkylsulfonates or C 1 -C 4 -alkyl phenylsulfonates,
• Very preferred alkylating agents are C 1 -C 6 -alkyl halides, di-C 1 -C 6 -alkyl sulfates, C 1 -C 4 -alkyl C 1 -C 6 -alkylsulfonates or C 1 -C 4 -alkyl phenylsulfonates.
• alkylating agents are C 1 -C 6 -alkyl halides, di-C 1 -C 6 -alkyl sulfates, di-C 1 -C 6 -alkyl carbonates, C 1 -C 4 -alkyl C 1 -C 6 -alkylsulfonates or C 1 -C 4 -alkyl phenylsulfonates.
• alkylating agents are C 1 -C 6 -alkyl halides and di-C 1 -C 6 -alkyl sulfates; most preferably di-C 1 -C 6 -alkyl sulfates.
• alkylating agents are C 1 -C 6 -alkyl halides, di-C 1 -C 6 -alkyl sulfates and di-C 1 -C 6 -alkyl carbonates; very preferably C 1 -C 6 -alkyl halides and di-C 1 -C 6 -alkylsulfates; most preferably di-C 1 -C 6 -alkyl sulfates.
• alkylating agents are methylating agents or ethylating agents, such as methyl iodide, ethyl iodide, methyl bromide, methyl chloride, ethyl bromide, ethyl chloride, dimethyl sulfate, diethyl sulfate, methyl or ethyl C 1 -C 6 -alkylsulfonate or the methyl or ethyl esters of the abovementioned phenylsulfonic acids.
• especially preferred alkylating agents are methylating agents or ethylating agents, such as methyl iodide, ethyl iodide, methyl bromide, methyl chloride, ethyl bromide, ethyl chloride, dimethyl sulfate, dimethyl carbonate, diethyl sulfate, methyl or ethyl C 1 -C 6 -alkylsulfonates or the methyl or ethyl esters of the abovementioned phenylsulfonic acids.
• methylating agents or ethylating agents such as methyl iodide, ethyl iodide, methyl bromide, methyl chloride, ethyl bromide, ethyl chloride, dimethyl sulfate, dimethyl carbonate, diethyl sulfate, methyl or ethyl C 1 -C 6 -alkylsulf
• a very particularly preferred methylating agent is dimethyl sulfate.
• the alkylating agent can be employed both in an equimolar amount, based on the 3-phenyluracils of the formula II, and in a substoichiometric amount or superstoichiometric amount.
• At least an equimolar amount of the alkylating agent III, based on the 3-phenyluracils of the formula II is employed.
• the molar ratios for the ratio of 3-phenyluracils of the formula II to alkylating agent III are generally in the range from 1:1 to 1:3, preferably from 1:1 to 1:1.3.
• Suitable bases for the reaction according to the invention are all customary organic and inorganic bases.
• Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal or alkaline earth metal fluorides, such as cesium fluoride, alkali metal amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such
• Preferred bases are selected from the group consisting of alkali metal and alkaline earth metal hydroxides, such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal and alkaline earth metal oxides, such as calcium oxide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, zinc carbonate, alkali metal bicarbonates, such as sodium bicarbonate and also ammonia or tertiary amines, such as triethylamine;
• alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide
• alkali metal and alkaline earth metal oxides such as calcium oxide
• alkali metal and alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, zinc carbonate
• alkali metal bicarbonates such as sodium bicarbonate and also ammoni
• alkali metal and alkaline earth metal hydroxides particularly preferably selected from the group consisting of alkali metal and alkaline earth metal hydroxides, ammonia and also tertiary amines.
• bases selected from the group consisting of alkali metal and alkaline earth metal hydroxides, such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal and alkaline earth metal oxides, such as calcium oxide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, zinc carbonate and also alkali metal bicarbonates, such as sodium bicarbonate.
• alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide
• alkali metal and alkaline earth metal oxides such as calcium oxide
• alkali metal and alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, zinc carbonate
• alkali metal bicarbonates such as sodium bicarbonate.
• the base used is sodium hydroxide or potassium hydroxide, sodium carbonate or potassium carbonate or sodium bicarbonate or potassium bicarbonate.
• the base used is an alkali metal hydroxide or alkaline earth metal hydroxide, preferably an alkali metal hydroxide.
• the bases are generally employed in equimolar amounts, based on the 3-phenyluracils of the formula II; however, they can also be employed in catalytic amounts, in excess or, if appropriate, as solvent.
• At least an equimolar amount of base is used.
• the amount of base is generally not more than 1.3 mol per mole of the compound II.
• the pH is, during the entire reaction, kept in the range from 1 to 6 by adding base a little at a time.
• the pH is, by adding base a little at a time, preferably kept in a range of from 2 to 6;
• “Adding base a little at a time” means that the addition of base during the reaction is in individual portions, i.e. in at least 2 portions, or in more than 2 up to many portions, or continuously.
• the pH can, during the reaction, be kept by different means by adding base a little at a time in the range from 1 to 6, these embodiments being particular embodiments of the process according to the invention, both on their own and in combination:
• the pH is adjusted to between 1 and 6 and then, during the reaction, kept constant at the value adjusted at the beginning.
• the pH adjusted to between 1 and 6 during the beginning of the reaction is continuously changed to another pH in the range from 1 to 6 during the reaction.
• the continuous change of the pH during the reaction is repeated, where this repetition may be carried out as many times as desired.
• the pH is initially, during the beginning of the reaction, adjusted to between 1 and 6 and initially kept constant at the adjusted value. After partial reaction, this is then changed to a different pH in the range of from 1 to 6, which is then again kept constant at the newly adjusted value.
• This newly adjusted pH can then, after partial reaction, again be changed to a different pH in the range of from 1 to 6, i.e. the adjusted pH in the range of from 1 to 6 can, after partial reaction, be changed as many times as desired.
• the pH adjusted to between 1 and 6 during the beginning of the reaction is changed one or more times, in each case after partial reaction, to a different pH in the range of from 1 to 6, the respective changed pH being kept constant until the next change.
• the pH adjusted to between 1 and 6 during the beginning of the reaction is changed once, after partial reaction, to a different pH in the range of from 1 to 6.
• the pH adjusted during the beginning of the reaction to between 1 and 6 may be higher than the pH value adjusted by the pH change or than the pH values adjusted by the pH changes.
• the pH adjusted during the beginning of the reaction to between 1 and 6 may be lower than the pH value adjusted by the pH change or than the pH values adjusted by the pH changes.
• the pH adjusted during the beginning of the reaction to between 1 and 6 may be in between the pH values adjusted by the pH changes.
• the pH adjusted during the beginning of the reaction to between 1 and 6 is higher than the pH value adjusted by the pH change or than the pH values adjusted by the pH changes.
• the person skilled in the art may determine the pH by standard methods, for example by periodic or continuous measurement of the pH.
• the 3-phenyluracils of the formula II, the alkylating agents of the formula III and the base can be brought into contact in any way per se, the base being added a little at a time.
• reaction partners and the base may be introduced into the reaction vessel and reacted separately, simultaneously or successively, the base being added a little at a time.
• the 3-phenyluracils of the formula II and the alkylating agents of the formula III are initially charged in a reaction vessel, if appropriate with the desired solvent, and the desired reaction conditions are then established by adding base a little at a time.
• reaction of the 3-phenyluracils II with the alkylating agent III is advantageously carried out in the presence of a solvent.
• Solvents suitable for these reactions are, depending on the temperature range, aliphatic, cycloaliphatic or aromatic hydrocarbons, such as pentane, hexane, cyclopentane, cyclohexane, toluene, xylene, chlorinated aliphatic and aromatic hydrocarbons, such as dichloromethane, trichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, 1,2-,1,3- or 1,4-dichlorobenzene, chlorotoluenes, dichlorotoluenes, open-chain dialkyl ethers, such as diethyl ether, di-n-propyl ether, diisopropyl ether, methyl tert-butyl ether, cyclic ethers, such as tetrahydrofuran, 1,4-dioxane, anisole, glycol ethers,
• Preferred solvents are N,N-dimethylformamide, N-methylpyrrolidone, acetone, dichloromethane, tetrahydrofuran, toluene, chlorobenzene, methyl acetate, ethyl acetate, butyl acetate or mixtures of these solvents.
• the alkylation of the 3-phenyluracils of the formula II is carried out at temperatures between ⁇ 5° C. and 100° C., preferably at temperatures between 0° C. and 80° C. and in particular at temperatures between 20° C. and 70° C., very preferably between 20° C. and 60° C.
• the reaction time can be determined by the person skilled in the art in a manner customary per se, by standard methods, such as thin-layer chromatography or HPLC.
• the reaction can be carried out at atmospheric pressure, reduced pressure or under elevated pressure, if appropriate under an inert gas, continuously or batchwise.
• reaction can also be carried out in a multiphasic system.
• the reaction is carried out in an aqueous/organic multiphasic system in the presence of phase-transfer catalysts.
• phase-transfer catalysts are quaternary ammonium salts, phosphonium salts, crown ethers or polyglycols.
• Suitable quaternary ammonium salts comprise, for example, tetra-(C 1 -C 18 )-alkylammonium fluorides, chlorides, bromides, iodides, tetrafluoroborates, diborates, hydrogensulfates, hydroxides, perchlorates and borates, such as, for example,
• phenyltri-(C 1 -C 18 )-alkylammonium chlorides bromides or fluorides, such as, for example,
• aromatic ammonium salts such as, for example, hexadecylpyridinium chloride,
• tetrabutylammonium chloride methyltributylammonium chloride, methyltrioctylammonium chloride, tetrabutylammonium bromide, tetrahexylammonium bromide, tetraoctylammonium bromide, tetrabutylammonium iodide, tetrahexylammonium iodide, tetrabutylammonium hydrogensulfate and tetrabutylammonium hydroxide.
• Suitable phosphonium salts comprise, for example,
• Suitable crown ethers comprise, for example, 18-crown-6, dibenzo-18-crown-6.
• the phase-transfer catalyst is employed in an amount of up to 20 mol %, preferably between 1 and 15 mol % and in particular between 2 and 12 mol %, based on the 3-phenyluracils II.
• the multiphasic system comprises an aqueous phase and at least one organic liquid phase.
• solid phases may also be present.
• the aqueous phase is preferably a solution of bases.
• Suitable bases for this preferred variant of the process according to the invention are all customary organic and inorganic bases as mentioned above, in particular the bases mentioned above as being preferred or particularly or very preferred.
• Preferred bases are alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; alkali metal and alkaline earth metal carbonates, such as lithium carbonate, sodium carbonate, potassium carbonate and calcium carbonate and alkali metal bicarbonates, such as sodium bicarbonate.
• alkali metal or alkaline earth metal hydroxides very preferably alkali metal hydroxides such as, for example, sodium hydroxide.
• the bases are generally employed in equimolar amounts, based on the 3-phenyluracils of the formula II; however, they can also be employed in catalytic amounts, in excess or, if appropriate, as solvents.
• At least an equimolar amount of base is employed.
• the amount of base is generally not more than 1.3 mol per mole of the compound II.
• the aqueous phase is particularly preferably a solution of bases, such as, for example, alkali metal or alkaline earth metal hydroxides, carbonates, alkali metal bicarbonates, ammonia or water-soluble primary, secondary or tertiary amines in water.
• bases such as, for example, alkali metal or alkaline earth metal hydroxides, carbonates, alkali metal bicarbonates, ammonia or water-soluble primary, secondary or tertiary amines in water.
• the aqueous phase is especially preferably a solution of alkali metal or alkaline earth metal hydroxides, carbonates or alkali metal bicarbonates in water.
• Preferred solvents for the organic phase are, depending on the temperature range, aliphatic, cycloaliphatic or aromatic hydrocarbons, such as pentane, hexane, cyclopentane, cyclohexane, toluene, xylene, chlorinated aliphatic and aromatic hydrocarbons, such as dichloromethane, trichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, 1,2-, 1,3- or 1,4-dichlorobenzene, chlorotoluenes, dichlorotoluenes, open-chain dialkyl ethers, such as diethyl ether, di-n-propyl ether, diisopropyl ether, methyl tert-butyl ether, cyclic ethers, such as tetrahydrofuran (THF) and anisole, aliphatic C 1 -C 6
• Preferred solvents for the organic phase are ethyl acetate, n-butyl acetate, chlorobenzene, THF, toluene or mixtures of these solvents; very preferred are ethyl acetate, n-butyl acetate, chlorobenzene and THF mixtures of these solvents, and also toluene and THF mixtures of toluene.
• Solid phases may occur during the reaction, for example if the 1-alkyl-3-phenyluracil of the formula I, the 3-phenyluracil of the formula II, the alkylating agent of the formula III, the base and/or the phase-transfer catalyst are not fully dissolved.
• the multiphasic system comprises, as aqueous phase, aqueous alkali metal hydroxide solution, for example, sodium hydroxide solution, and, as organic phase, toluene and tetrahydrofuran, or dichloromethane and tetrahydrofuran, chlorobenene and tetrahydrofuran, or ethyl acetate or n-butyl acetate.
• aqueous alkali metal hydroxide solution for example, sodium hydroxide solution
• organic phase toluene and tetrahydrofuran, or dichloromethane and tetrahydrofuran, chlorobenene and tetrahydrofuran, or ethyl acetate or n-butyl acetate.
• the 3-phenyluracils of formula II, the alkylating agents of the formula III, the base and, if appropriate, the phase-transfer catalyst can be brought into contact with one another in any manner per se, the base being added a little at a time.
• reaction partners, the base and, if appropriate, the phase-transfer catalyst can be introduced into the reaction vessel and reacted separately, simultaneously or successively, the base being added a little at a time.
• the 3-phenyluracils of the formula II may be initially charged in one of the organic solvents or solvent mixtures mentioned above. With mixing, the aqueous solution of the base, a little at a time, the alkylating agent III and, if appropriate, the phase-transfer catalyst are then added.
• the 3-phenyluracils of the formula II and the alkylating agents of the formula III and the phase-transfer catalyst are initially charged in a reaction vessel with the desired solvent, and the desired reaction conditions are then established by adding base a little at a time.
• the yield and the ratio of desired 3-phenyluracil I to unwanted dialkylation product A were determined by quantitative HPLC (symmetry C18 5 ⁇ m for 250 ⁇ 4.6 mm from waters; wavelength: 205 nm; mobile phase: gradient of A (0.1% by volume of H 3 PO 4 in H 2 O) and B (0.1% by volume of H 3 PO 4 in CH 3 CN); B increasing over 25 min from 35% to 100% and then over 2 min back to 35%; flow rate: 1 ml/min) or by qualitative HPLC (Symmetry C18 5 ⁇ m 250 ⁇ 4.6 mm from Waters; wavelength: 220 nm; mobile phase: 40% by weight of acetonitrile/60% by weight of water/0.1% by weight of 85% strength H 3 PO 4 ; flow rate: 1.5 ml/min).
• the mixture was stirred at 40° C. for 1 h, during which time further aqueous 10% strength NaOH solution was added, so that the pH was constant at the pH established beforehand. After 1 h, addition of the aqueous 10% strength NaOH solution was stopped, and the pH fell to 4.4-4.5. A further 0.9 g (0.0071 mol) of dimethyl sulfate was added, and the mixture was stirred for another 10 h at a pH of 4.4-4.5 and 40° C.
• the pH of the reaction mixture was then adjusted to 5.3-5.5. During the entire reaction time, more 10% strength aqueous solution of the base was added, so that during the entire course of the reaction the pH was constant at the pH adjusted beforehand.

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